Theoretical study of tris(o-phenylenedioxy) cyclotrisphosphazene (TPP) electronic structure with ab initio and DFT methods

Using HF and DFT-B3LYP methods, basis set dependence on the optimal geometry of tris(o-phenylenedioxy)cyclotriphosphazene has been investigated. It was found that polarized functions are necessary for an appropriate description of geometry characteristics and electronic structure of this compound. B3LYP/6-31G(d) optimized geometry was found to agree well with crystal data. The study of the electronic structure of the neutral molecule has shown that the frontier orbitals are strongly localized on the three spirocyclic side groups, while injection effect of charge on the structure of the molecule has small structural changes on it, implying a certain stability of the molecular structure.

[1]  P. C. Hariharan,et al.  The influence of polarization functions on molecular orbital hydrogenation energies , 1973 .

[2]  W. H. Barnes,et al.  X-ray crystallography of the phenyltriphosphonitriles. III. The crystal structure of 2,2,4,4,6,6-hexaphenylcyclotriphosphazatriene , 1969 .

[3]  Mark S. Gordon,et al.  Self-consistent molecular-orbital methods. 22. Small split-valence basis sets for second-row elements , 1980 .

[4]  A. J. Wagner,et al.  The crystal structure of compounds with (N–P)n rings. VII. Refinement of the crystal structure of hexabromocyclotriphosphazene N3P3Br6 , 1970 .

[5]  J. Pople,et al.  Self-consistent molecular orbital methods. 21. Small split-valence basis sets for first-row elements , 2002 .

[6]  M. Breza,et al.  On bonding in cyclic triphosphazenes , 2000 .

[7]  Mark S. Gordon,et al.  The isomers of silacyclopropane , 1980 .

[8]  G. J. Bullen.  An improved determination of the crystal structure of hexachlorocyclotriphosphazene (phosphonitrilic chloride) , 1971 .

[9]  D. K. Hazra,et al.  A Study on the Solvation Phenomena of Some Sodium Salts in 1,2-Dimethoxyethane from Conductance, Viscosity, Ultrasonic Velocity, and FT-Raman Spectral Measurements , 2001 .

[10]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[11]  S. Rettig,et al.  Crystal and molecular structure of hexamethylcyclotriphosphazene, (NPMe2)3 , 1977 .

[12]  J. Pople,et al.  Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules , 1971 .

[13]  J. Trotter,et al.  Crystal and molecular structure of hexaphenoxycyclotriphosphazene, [NP(OPh)2]3 , 1971 .

[14]  J. Pople,et al.  Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules , 1972 .

[15]  Michael J. Frisch,et al.  Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets , 1984 .

[16]  Aurora Costales,et al.  Topological Analysis of Chemical Bonding in Cyclophosphazenes , 2001 .

[17]  M. Breza.  The electronic structure of planar phosphazene rings , 2000 .

[18]  P. C. Hariharan,et al.  Accuracy of AH n equilibrium geometries by single determinant molecular orbital theory , 1974 .

[19]  Harry R. Allcock,et al.  Tris(o-phenylenedioxy)cyclotriphosphazene: the clathration-induced monoclinic to hexagonal solid-state transition , 1986 .

[20]  M. W. Dougill.  598. Phosphonitrilic derivatives. Part X. The crystal structure of trimeric phosphonitrilic fluoride , 1963 .

[21]  Timothy Clark,et al.  Efficient diffuse function‐augmented basis sets for anion calculations. III. The 3‐21+G basis set for first‐row elements, Li–F , 1983 .

[22]  I. Paul,et al.  Crystal and molecular structure of trimeric phosphonitrilic isothiocyanate , 1970 .